JP2002279917A - Crystalline conductive particulate, manufacturing method of the particulate, coating solution for transparent conductive film formation, base material with the transparent conductive film, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide crystalline conductive particulates that can be used in the formation of a base material with a transparent conductive film, having a low surface resistance of about 10<7> Ω/(square) or lower, of superior a antistatic property and an electromagnetic wave shielding property, having low luminous reflectance and excelling in an antireflective property, and to provide a manufacturing method of the particulate; and the like. SOLUTION: The crystalline conductive particulate has void ratio in the range of 0.10 to 0.60 ml/g. The manufacturing method of the crystalline conductive particulate comprises a step of adding a doping agent, if necessary, to a solution of metal salt in water and adding alkali to the mixture for hydrolysis to prepare hydrous oxide particles or doped hydrous oxide particles of the metal; a step of filtering and washing the hydrous oxide particles or doped hydrous oxide particles; a step of dispersing the washed hydrous oxide particles or doped hydrous oxide particles in water and maturing the solution at 50 to 350 deg.C; a step of filtering out and drying the metal hydroxide or doped hydrous oxide particles in the matured dispersion solution; and a step of baking the dried hydrous oxide particles or doped hydrous oxide particles at 200 to 800 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to crystalline conductive fine particles, a method for producing the fine particles, a coating solution for forming a transparent conductive film containing the fine particles, a substrate with a transparent conductive film, and the substrate. It relates to a display device. More specifically, since the crystalline conductive fine particles have holes or cavities on the outer surface and / or inside of the particles and have high crystallinity, the refractive index is low. The refractive index can be reduced without lowering the conductivity of the fine particle layer, and the difference in refractive index between the conductive fine particle layer and the transparent film formed on the layer can be reduced. Crystalline conductive fine particles having a low reflectance (broad reflectance curve) and capable of obtaining a substrate with a transparent conductive film having excellent antistatic properties, electromagnetic wave shielding properties, antireflective properties, etc., and a method for producing the fine particles , A coating solution for forming a transparent conductive film containing the fine particles,
The present invention relates to a substrate having a transparent conductive film and a display device including the substrate.

[0002]

2. Description of the Related Art Conventionally, for the purpose of preventing the surface of a transparent substrate such as a display panel such as a cathode ray tube, a fluorescent display tube and a liquid crystal display panel from being charged and antireflective, these surfaces have an antistatic function. Formation of a conductive film and a transparent film having an antireflection function has been performed.

Also, it is known that electromagnetic waves are emitted from a cathode ray tube or the like. In addition to the conventional antistatic and antireflection methods, these electromagnetic waves and the electromagnetic field formed due to the emission of the electromagnetic waves are covered by a conductive film. Shielding is also being done. The antistatic conductive film has a surface resistance of 1
0 ⁷ Ω / □ must have a surface resistance of degree, as the conductive film for electromagnetic shielding is necessary to have 10 ² ~10 ⁴ Ω / □ degree of surface resistivity.

[0004] The conductive film having the antistatic function is as follows:
For example, it is composed of a conductive oxide such as Sb-doped tin oxide or Sn-doped indium oxide, and can be obtained by applying and drying a coating solution containing such a conductive oxide. Further, the conductive film for shielding electromagnetic waves is made of, for example, a metal such as Ag. For example, a conductive film forming coating liquid in which colloidal metal fine particles are dispersed in a polar solvent is applied to the surface of the substrate, It can be formed by drying.

Further, the transparent coating for the purpose of preventing reflection is usually made of a low refractive index material such as silica.
It is usually formed on the surface of the conductive film by a known method such as a method D or a coating method. By the way, in such a substrate with a transparent coating, in the visible light (wavelength range: 400 to 700 nm) region,
Although the bottom reflectivity (reflectance at the wavelength having the lowest reflectance in the wavelength range of 400 to 700 nm) is about 1%,
In the wavelength region near 400 nm and 700 nm, the reflectance becomes high, and therefore reflection (reflection) and coloring are recognized, and there is a problem in that the display performance is poor such as part of the image being unclear. At the same time, a reduction in luminous reflectance (average reflectance over the entire visible light range) is required.

The present inventors have further studied a transparent conductive film excellent in antireflection performance, and as a result, as a conductive fine particle, a crystalline conductive film having holes and / or cavities on the outer surface and / or inside of the particle. By using the conductive fine particles, the conductivity can be maintained, and the refractive index of the conductive fine particles can be reduced. As a result, the obtained substrate with a transparent conductive film maintains high antistatic performance and electromagnetic wave shielding performance. In addition, they have found that the luminous reflectance is low and the antireflection performance is excellent, and have completed the present invention.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, has a low surface resistance of about 10 ⁷ Ω / □ or less, is excellent in antistatic properties and electromagnetic wave shielding properties, and has a high visual sensitivity. Crystalline conductive fine particles that can be used for forming a substrate with a transparent conductive film having a low reflectance and excellent antireflection performance, a method for producing the fine particles, a coating liquid for forming a transparent conductive film containing the fine particles, and a transparent liquid It is an object of the present invention to provide a substrate provided with a conductive film and a display device provided with the substrate.

[0008]

SUMMARY OF THE INVENTION The crystalline conductive fine particles according to the present invention are characterized in that the porosity is in the range of 0.10 to 0.60 ml / g. The crystalline conductive fine particles are preferably tin oxide, tin oxide doped with Sb, F or P, indium oxide, indium oxide doped with Sn or F, antimony oxide, lower titanium oxide or a mixture thereof.

The method for producing crystalline conductive fine particles according to the present invention comprises the following steps (a) to (e): (a) a doping agent is added to a metal salt aqueous solution, if necessary, Step of preparing hydrated oxide particles or doped hydrated oxide particles of the metal by adding an alkali and hydrolyzing (b) filtering and washing the hydrated oxide particles or the doped hydrated oxide particles Step (c) dispersing the washed hydrated oxide particles or doped hydrated oxide particles in water and aging the same at 50 to 350 ° C. (d) hydrating oxide particles or doping from the aged dispersion (E) a step of baking the dried hydrated oxide particles or the doped hydrated oxide particles at 200 to 800 ° C.

The metal salt is a metal salt of one metal selected from Sn, In, Sb and Ti, and the doping agent is
It is preferably a compound containing one element selected from b, F and P. The coating liquid for forming a transparent conductive film according to the present invention comprises the crystalline conductive fine particles and a polar solvent.

A substrate with a transparent conductive film according to the present invention is provided on a substrate, a transparent conductive fine particle layer containing the crystalline conductive fine particles on the substrate, and provided on the transparent conductive fine particle layer; It is composed of a transparent film having a lower refractive index than the transparent conductive fine particle layer.

A display device according to the present invention is characterized in that the display device includes a front plate made of the base material with the transparent conductive film, and a transparent conductive film is formed on an outer surface of the front plate.

[0013]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. First, the crystalline conductive fine particles according to the present invention will be described. The crystalline conductive fine particles according to the present invention have 0.10 to 0.1.
60 ml / g, preferably 0.15 to 0.50 ml / g
Has a porosity in the range.

The porosity of the crystalline conductive fine particles is 0.10 m
If it is less than 1 / g, the effect of lowering the refractive index of the conductive fine particle layer is insufficient, the effect of lowering the luminous reflectance is not sufficiently obtained, and the porosity of the crystalline conductive fine particles is 0. .
If it exceeds 60 ml / g, the conductivity of the conductive fine particles may decrease, and the antistatic performance may be insufficient. The porosity of such crystalline conductive fine particles can be determined as follows.

For a sample obtained by heating crystalline conductive fine particles at 200 ° C. for 2 hours, a nitrogen adsorption isotherm at the temperature of liquid nitrogen was determined, and the nitrogen adsorption in a range of relative pressure corresponding to a hole diameter of 1 nm to 20 nm was determined. The adsorption volume (ml / g) is determined as the porosity. As an example of such crystalline conductive fine particles, FIG. 1 shows a transmission electron micrograph (TEM photograph) of the crystalline conductive fine particles obtained in Example 1 described later. In FIG. 1, holes and cavities are portions having a light color tone.

The crystalline conductive fine particles can be used without particular limitation as long as they have conductivity and have the above-mentioned characteristics. However, the crystalline conductive fine particles used in the present invention include oxidized fine particles. It is preferably tin oxide, indium oxide doped with tin, Sb, F or P, indium oxide doped with Sn or F, antimony oxide, lower titanium oxide, or a mixture thereof.

The crystalline conductive fine particles according to the present invention have an average particle diameter in the range of 2 to 200 nm, preferably 4 to 150 nm.
in the range of nm. When the average particle diameter of the crystalline conductive fine particles is less than 2 nm, it is difficult to obtain crystalline conductive fine particles capable of effectively lowering the refractive index because the particles are too small and the porosity is small. Also, if the porosity is increased with small particles, the crystallinity becomes insufficient and the conductivity may not be sufficiently exhibited. On the other hand, if the particle size is too small, the surface resistance of the particle layer increases rapidly because the grain boundary resistance increases, and the antistatic performance and electromagnetic wave shielding performance may be insufficient.

The average particle diameter of the crystalline conductive fine particles is 200
When the thickness exceeds nm, the stability of the coating solution for forming the transparent conductive film decreases, the formability of the film, the adhesion to the substrate, the strength of the film, and the like are reduced. The light transmittance of the particle layer may decrease or the haze may increase. The crystalline conductive fine particles of the present invention have a hole (in the case of the external surface) or a cavity (in the case of the internal) on the external surface and / or inside. The sizes of the holes and the cavities are not particularly limited, and usually have a diameter of 1 to 20 nm, preferably 1 to 10 nm.
When the diameter of the hole or the cavity is less than 1 nm, the particles themselves are dense, the porosity is less than 0.10 ml / g, and the refractive index of the conductive fine particle layer is not sufficiently low, so that the effect of lowering the luminous reflectance is reduced. May not be obtained.

The crystalline conductive fine particles according to the present invention may have either a hole or a cavity, or may have both. The diameter of such a hole or cavity can be determined by taking a TEM photograph, measuring the major axis and the minor axis, and determining the average value. It is desirable that the crystalline conductive fine particles according to the present invention have a crystallinity of 0.9 to 1.3, preferably 1 to 1.25. Crystallinity is 0.
If it is less than 9, the conductivity is insufficient and the antistatic effect may not be sufficiently obtained. Further, it is difficult to obtain crystalline conductive fine particles having a crystallinity of 1.3 or more, and even if obtained, the porosity tends to be insufficient.

The above crystallinity can be determined as follows. The X-ray diffraction spectrum of the crystalline conductive fine particle powder is measured, and the peak height of the diffraction intensity (Ic)
Is compared with the similar peak height (Is) of the standard sample (1), and is determined as follows. Crystallinity = Ic / Is As the standard sample (1), one having a porosity of substantially zero is used. For example, in the method for producing crystalline conductive fine particles in Examples described later, the same composition is used. The conductive fine particles obtained without going through the aging step
Used for 5 hours.

The crystalline conductive fine particles preferably have a volume resistivity of about 0.1 Ω · cm or less.
If the crystalline conductive fine particles have a volume resistivity in the above range,
The resulting substrate with a transparent conductive film has a surface resistance of 10 ² to
In the range of 10 ⁷ Ω / □, it is possible to obtain a substrate with a transparent conductive film having sufficient antistatic performance and electromagnetic wave shielding performance depending on the film thickness. For example, when the crystalline conductive fine particles are indium oxide doped with Sn or F, a base material having a transparent conductive film having a surface resistance in a range of approximately 10 ² to 10 ⁴ Ω / □ can be formed, and thus, antistatic can be achieved. In addition to the performance, the electromagnetic field generated due to the emission of the electromagnetic wave can be effectively shielded. In addition, crystalline conductive fine particles,
In the case of tin oxide, indium oxide, tin oxide doped with Sb, F or P, antimony oxide, or low-order titanium oxide, a transparent conductive film having a surface resistance of approximately 10 ⁴ to 10 ⁷ Ω / □ can be formed. And excellent antistatic performance.

Such crystalline conductive fine particles can be obtained, for example, by the following manufacturing method. Next, a method for producing the crystalline conductive fine particles of the present invention will be described. The method for producing crystalline conductive fine particles of the present invention comprises the following steps (a) to (e).

Step (a): A doping agent is added to the aqueous metal salt solution, if necessary, and an alkali is added thereto to hydrolyze the hydrated oxide particles or doped hydrated oxide particles of the metal. Prepare. The metal salt can be used without particular limitation as long as a desired oxide precursor (that is, hydroxide) can be obtained.
As the oxide, tin oxide, indium oxide, antimony oxide, lower titanium oxide or a mixture thereof is preferable, and specific examples of the metal salt include tin chloride, tin nitrate, tin sulfate, indium chloride, indium nitrate, and sulfuric acid. Indium, antimony chloride, antimony nitrate, antimony sulfate, titanium tetrachloride, titanium trichloride, titanium nitrate, titanyl sulfate and the like are preferably used.

As the doping agent, the oxide is tin oxide,
In the case of indium oxide, there is no particular limitation as long as it can be doped with Sb, Sn, F or P. As described above, tin oxide, Sb, F
Or P-doped tin oxide, indium oxide, Sn or F-doped indium oxide,
Antimony oxide, lower titanium oxide or a mixture thereof, for example, antimony chloride, antimony nitrate, tin chloride,
Tin nitrate, calcium fluoride, phosphoric acid and the like are used.

If necessary, the above-mentioned doping agent is added to the aqueous solution of the metal salt, and an alkali is added thereto to carry out hydrolysis to prepare hydrated oxide particles or hydrated oxide particles containing a doping agent. The concentration of the aqueous metal salt solution is 0.5 to 30% by weight as a metal oxide, and more preferably 5 to 20% by weight.
Is preferably within the range.

When the concentration of the aqueous metal salt solution is less than 0.5% by weight, the yield and production efficiency of the hydrated oxide particles are low due to the low concentration, and when the concentration of the aqueous metal salt solution exceeds 30% by weight. In some cases, the crystallinity after ripening described below does not exceed 0.9 and does not increase, and holes and cavities of the finally obtained crystalline conductive fine particles may not be sufficiently formed. Also,
The amount of the doping agent to be added as necessary depends on the type of the hydrated oxide particles or the doping agent. However, like the conventionally known conductive oxide containing a doping agent, the metal oxide is usually used as the oxide. Is preferably in the range of 1 to 20% by weight, more preferably 2 to 10% by weight.

When the amount of the dopant is within the above range, crystalline conductive fine particles having high conductivity can be obtained without impairing the crystallinity. The alkali to be added is not particularly limited as long as the metal salt can be hydrolyzed, and an alkali metal aqueous solution such as an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution, an aqueous ammonia solution, and a basic compound such as a quaternary amine may be used. it can. The amount of such an alkali added is not particularly limited as long as a hydrated oxide is obtained, but may be usually added so that the pH of the aqueous solution is in the range of 7 to 13. The temperature of the aqueous solution during hydrolysis is usually room temperature, but it can be heated or cooled as necessary.

If the pH of the aqueous solution is less than 7, the conductive fine particles finally obtained tend to be dense, the porosity is reduced, and the effect of lowering the refractive index may not be obtained. When the pH of the aqueous solution is in the above range, the crystallinity is high,
Crystalline conductive fine particles having a porosity in the range of 0.10 to 0.60 ml / g can be obtained. Step (b): The prepared hydrated oxide particles or doped hydrated oxide particles are then washed.

The washing method is not particularly limited as long as impurities such as cations and anions derived from the metal salt, the doping agent and the added alkali can be removed, and the washing can be carried out by a conventionally known method. Specifically, a normal filtration and washing method, an ultrafiltration membrane method and the like are suitable. The amount of impurities after washing is preferably 1% by weight or less, more preferably 0.5% by weight or less, in the hydrated oxide particles or the hydrated oxide particles containing a doping agent. When the amount of impurities is 1% by weight or less, the crystallinity and conductivity are high,
Crystalline conductive fine particles having a porosity in the range of 10 to 0.60 ml / g can be obtained.

Step (c): Aged and washed hydrated oxide particles or hydrated oxide particles containing a doping agent are dispersed in water and aged at 50 to 350 ° C., preferably 60 to 250 ° C. By this aging step, the crystallinity of the hydrated oxide particles or the hydrated oxide particles containing the doping agent is increased, and holes and / or cavities of the finally obtained conductive oxide particles are formed.

The concentration of the hydrated oxide particles or the hydrated oxide particles containing the doping agent in the aqueous dispersion is from 1 to 1 when the hydrated oxide particles or the hydrated oxide particles containing the doping agent are converted into the oxide. It is preferably in the range of 20% by weight, more preferably 2 to 10% by weight. The concentration of the hydrated oxide particles or the hydrated oxide particles containing the dopant is 1 in terms of oxide.
When the amount is less than the weight percentage, the particle growth rate is low, and the resulting crystalline conductive fine particles may have a fine or non-uniform particle size, or may have insufficient crystallinity.

If the concentration of the hydrated oxide particles or the hydrated oxide particles containing the doping agent exceeds 20% by weight, the particles tend to aggregate, and the porosity of the finally obtained crystalline conductive fine particles is small. Therefore, the effect of lowering the refractive index of the conductive fine particle layer tends to be insufficient. When the aging temperature is lower than 50 ° C., although depending on the aging time, the particle growth rate is slow, and the obtained crystalline conductive fine particles have a fine or non-uniform particle size, or the crystallinity is poor. May be sufficient.

When the aging temperature exceeds 350 ° C., the crystalline conductive fine particles finally obtained have almost no voids such as holes and cavities, and the effect of lowering the refractive index of the conductive fine particle layer cannot be obtained. . The aging time varies depending on the aging temperature, but is usually 0.5 to 48 hours.

In the method for producing crystalline conductive fine particles of the present invention, the crystallinity of the aged hydrated oxide particles or the hydrated oxide particles containing a doping agent is important, and the crystallinity at this time is 1 or more. , Preferably 1.1 or more. When the crystallinity of the aged particles is less than 1, the crystallinity of the finally obtained crystalline conductive fine particles is insufficient, and the fine particles having the porosity as described above cannot be obtained. is there.

The average particle diameter of the hydrated oxide particles after aging or the hydrated oxide particles containing a doping agent is not particularly limited, but is generally preferably in the range of 2 to 200 nm. The average particle diameter of the hydrated oxide particles after aging or the hydrated oxide particles containing a doping agent is 2 nm.
If it is less than 1, crystalline conductive fine particles having a high porosity are difficult to generate, and the effects of the present invention cannot be obtained.

If the average particle diameter of the hydrated oxide particles after aging or the hydrated oxide particles containing a dopant exceeds 200 nm, a coating for forming a conductive fine particle layer using the obtained crystalline conductive fine particles. The stability of the liquid may be reduced, the transparency of the conductive fine particle layer may be reduced, or the adhesion between the conductive fine particle layer and the substrate may be insufficient. The crystallinity of the hydrated oxide particles after aging or the hydrated oxide particles containing a doping agent is determined as follows.

The particles were dried at 105 ° C. for 5 hours, the X-ray diffraction spectrum of the dried fine particle powder was measured, and the height (Ica) of the peak having the highest diffraction intensity was determined by the same peak as that of the standard sample (II). And the height is calculated as follows. Crystallinity = Ica / Isa The standard sample (II) is a hydrated oxide particle having the same composition or a hydrated oxide containing a doping agent in the method for producing crystalline conductive fine particles of the present invention described later. The particles obtained by drying the particles at 105 ° C. for 5 hours are used.

Step (d) Separation / Drying The hydrated oxide particles or the hydrated oxide particles containing a doping agent are separated from the dispersion liquid after the aging by filtration and dried. The drying temperature is not particularly limited as long as it is a temperature at which the solvent evaporates. In the drying treatment, the baking treatment in the next step may be performed without completely drying the hydrated oxide particles or the hydrated oxide particles containing the doping agent.

Step (e) Firing The dried hydrated oxide particles or hydrated oxide particles containing a doping agent are fired at 200 to 800 ° C. When the calcination temperature of the hydrated oxide particles or the hydrated oxide particles containing the doping agent is lower than 200 ° C., sufficient conductivity may not be obtained due to the remaining crystallization water.

If the sintering temperature exceeds 800 ° C., holes and / or cavities may disappear and a sufficient porosity may not be obtained. May be impaired. In the method for producing crystalline conductive fine particles of the present invention, the step
After (d) and / or step (e), it may be ground to a desired size, if necessary. As a pulverizing method, a conventionally known method such as a ball mill and a sand mill can be suitably adopted. During grinding, acids such as nitric acid and hydrochloric acid,
The pH may be adjusted with an alkali such as sodium hydroxide, potassium hydroxide, ammonia, or the like, and may be further treated with an ion exchange resin after pulverization to remove impurity (acid, alkali) ions.

Next, the coating solution for forming a transparent conductive film according to the present invention will be described. The coating liquid for forming a transparent conductive film according to the present invention comprises crystalline conductive fine particles and a polar solvent.
As the crystalline conductive fine particles, those described above can be used.

According to the present invention, the crystalline conductive fine particles are contained in an amount of 0.1 to 10% by weight in the coating liquid for forming a transparent conductive film.
Preferably, it is contained in the range of 0.5 to 5% by weight. When the concentration of the crystalline conductive fine particles in the coating liquid for forming a transparent conductive film is less than 0.1% by weight, the film thickness of the obtained film may be small, and sufficient conductivity may not be obtained.

When the concentration of the crystalline conductive fine particles in the coating solution for forming a transparent conductive film exceeds 10% by weight, the stability of the coating solution is reduced, or the film thickness is increased and the light transmittance is reduced. The transparency tends to deteriorate and the appearance tends to deteriorate.
Examples of the polar solvent include water; alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol and hexylene glycol; and methyl acetate, ethyl acetate, and the like. Esters: ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, acetylacetone, and acetoacetate; No. These may be used alone or as a mixture of two or more.

Such a coating liquid for forming a transparent conductive film may contain conductive fine particles other than the crystalline conductive fine particles. As the conductive fine particles other than the crystalline conductive fine particles, conventionally known metal fine particles such as Ag and Ag-Pd, alloy fine particles, and fine carbon particles can be used. The average particle size of the conductive fine particles other than the crystalline conductive fine particles is also 1 to 200 nm, preferably 2 to 15 nm.
It is preferably in the range of 0 nm.

The coating liquid for forming a transparent conductive film according to the present invention may contain a matrix-forming component which acts as a binder (also referred to as a matrix) for the crystalline conductive fine particles after the film is formed. As such a matrix forming component, specifically, a hydrolyzed polycondensate of an organosilicon compound such as an alkoxysilane or a silicic acid polycondensate obtained by de-alkalizing an aqueous alkali metal silicate solution, or (polyester resin , Urethane resin, epoxy resin, acrylic resin, alkyd resin) and the like. The matrix-forming component is contained in an amount of 0.01 per part by weight of the crystalline conductive fine particles.
It may be contained in an amount of 0.5 to 0.5 parts by weight, preferably 0.03 to 0.3 parts by weight. Further, a curing catalyst may be included.

Further, the coating liquid for forming a transparent conductive film of the present invention contains an organic stabilizer in the coating liquid for forming a transparent conductive film in order to improve the dispersibility and stability of the crystalline conductive fine particles. May be included. Specific examples of such organic stabilizers include gelatin, polyvinyl alcohol, polyvinylpyrrolidone, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and citric acid. And its salts, heterocyclic compounds and mixtures thereof.

Such an organic stabilizer may be contained in an amount of 0.005 to 0.5 part by weight, preferably 0.01 to 0.2 part by weight, based on 1 part by weight of the crystalline conductive fine particles. . When the amount of the organic stabilizer is less than 0.005 parts by weight, sufficient dispersibility and stability may not be obtained. When the amount is more than 0.5 parts by weight, conductivity may be impaired. is there. Further, a dye, a pigment, and the like may be added to the coating liquid for forming a transparent conductive film so that the visible light transmittance is constant in a wide wavelength range of visible light.

The solid content concentration in the coating liquid for forming a transparent conductive film used in the present invention (the conductive fine particles other than the crystalline conductive fine particles and the crystalline conductive fine particles added as necessary, dyes, pigments, etc.) The total amount of additives) is the fluidity of the liquid,
From the viewpoint of the dispersibility of particulate components such as crystalline conductive fine particles in the coating liquid, the content is preferably 15% by weight or less, preferably 0.1% by weight.
It is preferably 15 to 5% by weight.

Next, the substrate with a transparent conductive film according to the present invention will be specifically described. In the substrate with a transparent conductive film according to the present invention, transparent conductive fine particles containing the crystalline conductive fine particles formed on a substrate such as a film, a sheet, or another molded body made of glass, plastic, ceramic, or the like. And a transparent film provided on the transparent conductive fine particle layer and having a lower refractive index than the transparent conductive fine particle layer.

[Transparent conductive fine particle layer] As the crystalline conductive fine particles, those described above can be used.
The transparent conductive fine particle layer has a thickness of about 5 to 200 nm, preferably 10 to 150 nm,
When the film thickness is in this range, a substrate with a transparent conductive film having excellent antistatic performance and electromagnetic wave shielding performance and particularly low luminous reflectance and excellent antireflection performance can be obtained.

Such a transparent conductive fine particle layer may contain conductive fine particles other than the above-mentioned crystalline conductive fine particles, a binder, and an organic stabilizer, if necessary. Specific examples of the conductive fine particles other than the crystalline conductive fine particles and the organic stabilizer include those similar to those exemplified in the coating liquid for forming a transparent conductive film. Further, as the binder, silica derived from a hydrolytic polycondensate of an organosilicon compound as the matrix-forming component, a silicic acid polycondensate, or the like, a resin for paint, or the like is used.

In the present invention, two or more transparent conductive fine particle layers having different transparent conductive fine particle layers may be laminated. In the case of laminating, it is preferable to decrease the refractive index sequentially from the layer on the substrate side to the outside. [Transparent coating] In the substrate with a transparent conductive coating according to the present invention,
A transparent film having a lower refractive index than the transparent conductive fine particle layer is formed on the transparent conductive fine particle layer.

The thickness of the formed transparent film is 50 to 30.
0 nm, preferably in the range of 80 to 200 nm. Such a transparent film is formed of, for example, an inorganic oxide such as silica, titania, and zirconia, and a composite oxide thereof. In the present invention, as the transparent film, a hydrolytic polycondensate of a hydrolyzable organosilicon compound, or a silica-based film composed of a silicic acid polycondensate obtained by dealkalization of an aqueous alkali metal silicate solution is particularly preferred. The substrate with a transparent conductive film on which such a transparent film is formed has excellent antireflection performance.

Further, when such a transparent film is mixed and used with a composite oxide particle having a refractive index of 1.44 or less as proposed in Japanese Patent Application Laid-Open No. Hei 7-133105 by the present applicant, the resulting transparent film is obtained. A substrate with a transparent conductive film having a low refractive index and excellent antireflection performance can be obtained. In addition, the transparent coating may contain additives such as fine particles, dyes, and pigments made of a low refractive index material such as magnesium fluoride, if necessary.

In the present invention, two or more transparent films having different transparent films may be laminated. When laminating a transparent film, it is preferable to decrease the refractive index sequentially from the inner coating to the outer coating. Method for Manufacturing Substrate with Transparent Conductive Film Next, a method for manufacturing the substrate with a transparent conductive film according to the present invention will be described.

The substrate with a transparent conductive film is coated with the above-mentioned coating solution for forming a transparent conductive film on a substrate and dried to form a layer of transparent conductive fine particles. It can be obtained by applying a coating solution for forming a film to form a transparent film having a lower refractive index than the fine particle layer on the transparent conductive fine particle layer. The coating liquid for forming the transparent conductive film used is composed of alkali metal ions, ammonium ions, polyvalent metal ions, inorganic anions such as mineral acids, and organic anions such as acetic acid and formic acid. It is desirable that the total amount of the concentration is small, specifically, 1 to 100 g of the solid content in the coating solution.
Desirably, the amount is 0 mmol or less. In order to reduce the ion concentration, for example, the material may be treated with an anion exchange resin, a cation exchange resin, activated carbon or the like.

As a method for forming the transparent conductive fine particle layer, for example, a coating solution for forming a transparent conductive film is dipped, spinnered, sprayed, roll-coated,
After applying it on the substrate by a method such as flexographic printing,
Dry at a temperature ranging from normal temperature to about 90 ° C. When the matrix forming component as described above is contained in the coating liquid for forming a transparent conductive film, the matrix forming component may be cured.

Specifically, the coating film formed by applying such a coating liquid for forming a transparent coating film is heated at 150 ° C. or more at the time of drying or after drying, or the uncured film is exposed to visible light. Electromagnetic waves such as ultraviolet rays, electron beams, X-rays, and γ-rays having a short wavelength may be irradiated, or may be exposed to an atmosphere of an active gas such as ammonia. By doing so, the curing of the film-forming component is promoted, and the hardness of the obtained transparent conductive fine particle layer is increased.

The thickness of the transparent conductive fine particle layer formed by the above method is preferably in the range of about 50 to 200 nm. A substrate can be obtained. Next, on the transparent conductive fine particle layer formed as described above,
A transparent film having a lower refractive index than the fine particle layer is formed.

The thickness of the transparent coating is preferably in the range of 50 to 300 nm, and more preferably in the range of 80 to 200 nm. When the thickness is in such a range, excellent antireflection properties are exhibited. There is no particular limitation on the method of forming the transparent film, and depending on the material of the transparent film, a dry thin film forming method such as a vacuum evaporation method, a sputtering method, or an ion plating method, or a dipping method or a spinner method as described above. And a wet thin film forming method such as a spray method, a roll coater method, and a flexographic printing method.

When the transparent film is formed by a wet thin film forming method, a conventionally known coating liquid for forming a transparent film can be used. Examples of such a coating liquid for forming a transparent film include:
Specifically, a coating liquid containing an inorganic oxide such as silica, titania, or zirconia, or a composite oxide thereof as a transparent film forming component is used. In the present invention, a coating solution for forming a silica-based transparent film containing a hydrolyzable polycondensate of a hydrolyzable organosilicon compound or a silicic acid solution obtained by dealkalizing an aqueous solution of an alkali metal silicate is used as a coating solution for forming a transparent film. The liquid is preferable, and particularly preferably contains a hydrolyzed polycondensate of an alkoxysilane represented by the following general formula [1]. The silica-based coating formed from such a coating solution has a smaller refractive index than the conductive fine particle layer containing the composite metal fine particles, and the resulting substrate with a transparent coating has excellent antireflection properties.

R _a Si (OR ′) _4-a [1] (wherein R is a vinyl group, an aryl group, an acryl group, an alkyl group having 1 to 8 carbon atoms, a hydrogen atom or a halogen atom, vinyl group, an aryl group, an acrylic group, an alkyl group of carbon-based number _{1~8, -C 2 H 4 OC n} H 2n + 1 (n = 1
To 4) or a hydrogen atom, and a is an integer of 1 to 3. Examples of such alkoxylans include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraoctylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltriisopropoxysilane , Vinyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane and the like.

When one or more of the above-mentioned alkoxysilanes are hydrolyzed in, for example, a water-alcohol mixed solvent in the presence of an acid catalyst, a coating liquid for forming a transparent film containing a hydrolyzed polycondensate of the alkoxysilane is obtained. Is obtained. The concentration of the film forming component contained in such a coating solution is preferably 0.5 to 2.0% by weight in terms of oxide. The coating solution for forming a transparent film used in the present invention is subjected to a deionization treatment in the same manner as in the case of the coating solution for forming a transparent conductive film, and the ionic concentration of the transparent conductive coating solution is changed to the value for forming the transparent conductive film. It may be reduced to the same level as the concentration in the application liquid.

Further, in such a coating liquid for forming a transparent film, a composite oxide particle having a refractive index of 1.44 or less proposed in Japanese Patent Application Laid-Open No. Hei 7-133105 by the present applicant is blended and used. The refractive index of the resulting transparent film is low,
Further, a substrate with a transparent conductive film having excellent antireflection performance can be obtained. Furthermore, the coating liquid for forming a transparent film used in the present invention contains fine particles composed of a low refractive index material such as magnesium fluoride, and a small amount of conductive material that does not impair the transparency and antireflection performance of the transparent film. Fine particles and / or additives such as dyes or pigments may be included.

In the present invention, the coating film formed by applying such a coating liquid for forming a transparent film is heated at 150 ° C. or more at the time of drying or after drying, or the uncured film has a wavelength shorter than that of visible light. Irradiation with electromagnetic waves such as ultraviolet rays, electron beams, X-rays, and γ-rays, or exposure to an active gas atmosphere such as ammonia. By doing so, the curing of the film-forming component is promoted, and the hardness of the obtained transparent film is increased.

Further, when a coating liquid for forming a transparent coating is applied to form a coating, the transparent conductive fine particle layer is applied to a thickness of about 40 to 9
Applying a coating liquid for forming a transparent film while maintaining the temperature at 0 ° C.
By performing the above-described treatment, ring-shaped irregularities are formed on the surface of the transparent film, and an antiglare substrate with a transparent film having less glare can be obtained. Next, a display device according to the present invention will be described.

The substrate with a transparent conductive film according to the present invention has a resistance of 10 ² to 10 ⁷ Ω / □ required for antistatic and electromagnetic wave shielding.
The substrate having a transparent conductive film having a surface resistance in the range described above and having sufficient antireflection performance in the visible light region and the near infrared region is suitably used as a front plate of a display device. The display device according to the present invention is a device for displaying an image electrically, such as a cathode ray tube (CRT), a fluorescent display tube (FIP), a plasma display (PDP), a liquid crystal display (LCD), and the like. A front plate made of a transparent base material with a transparent conductive film.

When a conventional display device having a front panel is operated, the base material is charged and dust or the like adheres to the substrate, and an image is displayed on the front panel, and simultaneously, an electromagnetic wave is emitted from the front panel. This electromagnetic wave may affect the human body of the observer. On the other hand, in the display device according to the present invention, since the full surface plate having the specific surface resistance is formed, the generated static electricity is effectively removed, and the electromagnetic waves emitted from the front plate are also effectively reduced. Removed. In particular, when the surface resistance of the front plate is approximately 10 ⁴ to 10 ⁷ Ω / □, the antistatic performance can be exhibited. When the surface resistance of the front plate is approximately 10 ² to 10 ⁴ Ω / □, In addition to the antistatic performance, it is possible to effectively shield an electromagnetic wave and an electromagnetic field generated by emission of the electromagnetic wave.

When reflected light is generated on the front plate of the display device, the reflected light makes it difficult to view a displayed image,
In addition, reflection that is perceived by the eyes when the luminous reflectance is large (reflection)
In some cases, it is difficult to suppress the coloring of the reflection color or to feel strongly, but in the display device according to the present invention, the conductive fine particle layer is formed using crystalline conductive fine particles having a low refractive index. Therefore, the difference in the refractive index between the transparent conductive fine particle layer and the transparent coating having a lower refractive index than the transparent conductive fine particle layer formed on the transparent conductive fine particle layer is small, and therefore, it is possible to effectively prevent reflected light. And the luminous reflectance is small, so that the reflection is weak and the coloring of the reflected color is suppressed.

[0070]

According to the present invention, a transparent conductive fine particle layer having an antistatic property, an electromagnetic wave shielding property and a low refractive index is formed, and the luminous reflectance (average reflectance over the entire visible light region) is formed together with the bottom reflectance. ), Which can be used as a substrate with a transparent conductive film having excellent antireflection performance.

According to the present invention, it can be used as a substrate with a transparent conductive coating having an anti-reflection property and having an anti-static property and an electromagnetic wave shielding property and having a transparent conductive fine particle layer having a low refractive index formed thereon. A method for producing crystalline conductive fine particles can be provided. Further, according to the present invention, a transparent conductive film for producing a substrate with a transparent conductive film having an antistatic performance, an electromagnetic wave shielding performance and a transparent conductive fine particle layer having a low refractive index and having an excellent antireflection performance is formed. Thus, a coating solution for forming a functional film can be obtained.

Further, according to the present invention, antistatic performance,
It is possible to obtain a substrate with a transparent conductive film having excellent anti-reflection performance and having an electromagnetic wave shielding performance and a transparent conductive fine particle layer having a low refractive index formed thereon. When such a substrate with a transparent conductive film is used as a front plate of a display device, a display device having excellent electromagnetic shielding properties and excellent antireflection properties can be obtained.

[0073]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0074]

Example 1 Preparation of conductive fine particles (P-1) A solution obtained by dissolving 79.9 g of indium nitrate in 686 g of water, and 12.7 g of potassium stannate as a doping agent
g was dissolved in a 10% by weight potassium hydroxide solution to prepare a solution, and these solutions were added to 1000 g of pure water maintained at 50 ° C. over 2 hours. During this time, the pH in the system was maintained at 11. The Sn-doped hydrated indium oxide particles were filtered and washed from the obtained Sn-doped hydrated indium oxide particle dispersion.

The washed Sn-doped indium oxide hydrate particles were suspended in pure water so that the concentration as an oxide became 10% by weight, and then aged at a temperature of 95 ° C. for 24 hours. The aged hydrate particles were dried at 105 ° C., and the crystallinity and the average particle size were measured. The crystallinity was evaluated by the method described above,
The particle size of the fine particles can be measured using a Microtrac particle size analyzer (by
Nikkiso). Table 1 shows the results.

Next, the aged hydrate particles were calcined in air at 350 ° C. for 3 hours, and further dried in a nitrogen gas atmosphere at 60 ° C.
By baking at 0 ° C. for 2 hours, Sn-doped indium oxide fine particles (P-1) were obtained. At this time, the crystallinity, average particle diameter, hole / cavity diameter, and porosity were measured. The crystallinity, average particle diameter, hole / cavity diameter, and porosity were evaluated by the methods described above.

Table 1 shows the results. The obtained Sn-doped indium oxide fine particles (P-1) were dispersed in pure water so as to have a concentration of 30% by weight, and the pH was further adjusted to 3.5 with an aqueous nitric acid solution.
Then, the mixture was pulverized with a sand mill for 3 hours while maintaining the mixture at 30 ° C. to prepare a sol. Next, this sol is treated with an ion exchange resin to remove nitrate ions,
Pure water was added to prepare a Sn-doped indium oxide fine particle (P-1) dispersion having a concentration of 20% by weight. The average particle diameter of the fine particles of the obtained dispersion was measured, and the results are shown in Table 1.

A part of the obtained fine particle dispersion was collected, dried, and observed with a TEM photograph. FIG. 1 shows a photograph of the obtained fine particles. As shown in FIG. 1, Sn-doped indium oxide fine particles having voids (cavities and holes) in the particles were obtained.

[0079]

Example 2 Preparation of conductive fine particles (P-2) A dispersion of Sn-doped indium oxide fine particles (P-2) was prepared in the same manner as in Example 1, except that the aging temperature was set at 180 ° C. The crystallinity and average particle size of the hydrated particles after aging, and the crystallinity, average particle size, hole / cavity diameter and porosity of the conductive fine particles after firing, and in the finally obtained dispersion liquid The average particle size of the conductive fine particles (P-2) was measured.

The results are shown in Table 1.

[0081]

Example 3 Preparation of Conductive Fine Particles (P-3) The procedure of Example 1 was repeated except that the aging temperature was 30 ° C.
An n-doped indium oxide fine particle (P-3) dispersion was prepared.
Crystallinity and average particle size of hydrated particles after aging, and crystallinity, average particle size, hole / cavity diameter and porosity of conductive fine particles after firing, and fine particles of finally obtained dispersion liquid Was measured for the average particle size (P-3).

The results are shown in Table 1.

[0083]

Comparative Example 1 Preparation of conductive fine particles (P-4) A dispersion of Sn-doped indium oxide fine particles (P-4) was prepared in the same manner as in Example 1, except that aging was not performed. Crystallinity and average particle size of hydrate at the time of preparation, crystallinity of conductive fine particles after firing, average particle size, hole / cavity diameter and porosity,
Furthermore, the average particle diameter of the fine particles (P-4) in the finally obtained dispersion was measured.

Table 1 also shows the results.

[0085]

Example 4 Preparation of conductive fine particles (P-5) 57.7 g of tin chloride and 7.0 of antimony chloride as a doping agent
g was dissolved in 100 g of methanol to prepare a solution.
The prepared solution was added to pure water 1 under stirring at 90 ° C. for 4 hours.
000 g, hydrolyzed, and filtered Sb-doped hydrated tin oxide from the resulting Sb-doped hydrated tin oxide dispersion.
Washed. Then, the washed Sb-doped hydrated tin oxide was
The suspension was suspended in pure water so that the concentration as an oxide became 20% by weight, and then aged at a temperature of 95 ° C. for 24 hours. The aged hydrate was dried at 105 ° C., and the crystallinity, average particle size, hole / cavity size, and porosity were measured. Table 1 shows the results.

Then, the mixture was calcined in air at 500 ° C. for 2 hours to obtain a conductive tin oxide powder (P-5) doped with Sb. The crystallinity and average particle size of the powder (P-5) were measured. Table 1 shows the results. 30 g of this powder was added to 70 g of an aqueous potassium hydroxide solution (containing 3.0 g as KOH), and the mixture was pulverized with a sand mill for 3 hours while maintaining the mixture at 30 ° C. to prepare a sol. Then, the sol is treated with an ion exchange resin, dealkalized, and pure water is added to the sol to obtain a 20 wt% Sb
A dispersion of doped tin oxide fine particles (P-5) was prepared.

The average particle size of the fine particles in the dispersion was measured. Table 1 shows the results.

[0088]

Comparative Example 2 Preparation of Conductive Fine Particles (P-6) A dispersion of Sn-doped indium oxide fine particles (P-6) was prepared in the same manner as in Example 4 except that ripening was not performed. Crystallinity and average particle size of hydrate particles at the time of preparation, crystallinity of conductive fine particles after firing, average particle size, hole / cavity diameter and porosity, and conductive fine particles in the dispersion (P-6 ) The average particle diameter of the fine particles was measured.

Table 1 shows the results.

[0090]

Example 5 Preparation of conductive fine particles (P-7) A solution obtained by dissolving 79.9 g of indium nitrate in 686 g of water was added to 1000 g of pure water maintained at 50 ° C.
Added over time. During this time, the pH in the system was maintained at 11. The hydrated indium oxide particles were separated from the obtained hydrated indium oxide particle dispersion by filtration and washed.

The washed hydrated indium oxide particles were suspended in pure water so that the concentration as an oxide was 10% by weight.
Then, aging was performed at a temperature of 95 ° C. for 24 hours. The aged hydrated indium oxide particles were dried at 105 ° C., and the crystallinity and the average particle size were measured. Next, the resultant was fired in air at 350 ° C. for 3 hours and further fired in a nitrogen gas atmosphere at 600 ° C. for 2 hours to obtain indium oxide fine particles (P-7). At this time, the crystallinity, average particle diameter, hole / cavity diameter, and porosity were measured. Table 1 shows the results.

This was dispersed in pure water to a concentration of 30% by weight, and the pH was adjusted to 3.5 with an aqueous nitric acid solution. Then, the mixture was pulverized with a sand mill for 3 hours while maintaining the mixture at 30 ° C. Thus, a sol was prepared. Next, this sol was treated with an ion exchange resin to remove nitrate ions, and pure water was added to prepare a dispersion of indium oxide fine particles (P-1) having a concentration of 20% by weight. The average particle size of the fine particles of the obtained dispersion was measured.

Table 1 shows the results.

[0094]

Comparative Example 3 Preparation of Conductive Fine Particles (P-8) Indium oxide fine particles (P-8) and a dispersion of indium oxide fine particles (P-8) were prepared in the same manner as in Example 5 except that aging was not performed. did. Crystallinity and average particle size of hydrate particles, crystallinity of conductive fine particles after firing, average particle size, hole / cavity diameter and porosity, and conductive fine particles in dispersion (P-8)
Was measured for the average particle size.

Table 1 shows the results.

[0096]

[Table 1]

[0097]

Examples 6 to 10, Comparative Examples 4 to 6 a) Transparent conductive film
Preparation of Coating Solution for Formation Dispersions of (P-1) to (P-8) shown in Table 1 and ethanol / 1-
Ethoxy-2-propanol (1: 1 weight ratio) was mixed to prepare coating liquids (C-1) to (C-8) for forming a transparent conductive film having a solid content of 3% by weight.

B) Preparation of a Coating Solution for Forming a Transparent Film A mixed solution of 50 g of ethyl orthosilicate (SiO ₂ : 28% by weight), 194.6 g of ethanol, 1.4 g of concentrated nitric acid and 34 g of pure water was stirred at room temperature for 5 hours. Thus, a liquid containing a matrix-forming component having an SiO ₂ concentration of 5% by weight was prepared. Then, a mixed solvent of ethanol / butanol / diacetone alcohol / isopropanol (2: 1: 1: 5 weight mixing ratio) was added thereto to prepare a coating liquid for forming a transparent film having a SiO ₂ concentration of 1% by weight.

C) Production of Panel Glass with Transparent Conductive Coating While maintaining the surface of the CRT panel glass (14 ″) at 40 ° C., the above-mentioned coating for forming a transparent conductive film was performed at 100 rpm for 90 seconds by a spinner method. Each of the liquids (C-1) to (C-8) was applied and dried, and then, on the transparent conductive fine particle layer thus formed, the same was applied by spinner method.
The coating solution for forming a transparent film was applied and dried under the conditions of 00 rpm and 90 seconds, and baked at 160 ° C. for 30 minutes to obtain a substrate with a transparent conductive film.

The surface resistance of these substrates having a transparent conductive film was measured with a surface resistance meter (LORESTA, manufactured by Mitsubishi Yuka Co., Ltd.), and the haze was measured by a haze computer (3000A, manufactured by Nippon Denshoku Co., Ltd.).
Was measured. The bottom reflectivity and the luminous reflectivity were measured using a reflectometer (MCPD-2000, manufactured by Otsuka Electronics Co., Ltd.), and the wavelength 4
In the range of 00 to 700 nm, the bottom reflectance at the wavelength having the lowest reflectance and the average reflectance in the above wavelength range were displayed as luminous reflectance.

The refractive index of the conductive fine particle layer was determined by using a silicon wafer instead of the CRT panel glass in the above c) and keeping the surface at 40 ° C. by spinner method at 100 rpm for 90 seconds. Each of the coating liquids (C-1) to (C-8) for forming a transparent conductive film is applied and dried.
Baking was performed at 60 ° C. for 30 minutes to form a conductive fine particle layer.
The refractive index of each conductive fine particle layer was measured with a spectroscopic ellipsometer.

The results are shown in Table 2. Further, a display device was assembled using the base material with the transparent conductive film obtained above, and the degree of reflection (reflection) and the degree of coloring of the fluorescent lamp at a distance of 5 m from the image and the image surface were observed as display performance. And evaluated according to the following criteria. Reflection (reflection) and coloring are weak, and the image is clear: ◎ Reflection (reflection) is weak but coloring is recognized, but the image is clear: ○ Reflection (reflection) and coloring are strong, and the image is strong A part of which is unclear: が Reflection (reflection) and coloring are strong, and reflection is clearer than the image: × The results are also shown in Table 2.

[0103]

[Table 2]

From the results in Table 2, it can be seen that the substrate with a transparent conductive film using the crystalline conductive fine particles according to the present invention has a low bottom reflectance, a low luminous reflectance and excellent antireflection performance. . Also, the display performance is excellent. On the other hand, the conductive fine particles having a low crystallinity and a small porosity as in Comparative Examples 1 to 3 have high bottom reflectance and luminous reflectance, and have insufficient antireflection performance. Further, the display performance is not always satisfactory.

[Brief description of the drawings]

FIG. 1 shows a transmission electron micrograph (TEM photograph) of crystalline conductive fine particles.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C01G 23/00 C01G 23/00 C 5G307 30/00 30/00 5G323 H01B 1/20 H01B 1/20 A 5 / 00 5/00 F 5/14 5/14 A 13/00 501 13/00 501Z 503 503B (72) Inventor Tsuguo Koyanagi 13-2 Kitaminato-cho, Wakamatsu-ku, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture Inside the Wakamatsu Plant (72) Inventor Toshiharu Hirai 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture Inside the Wakamatsu Plant, Catalyst Chemicals Co., Ltd. No. 13 No. 2 in the Wakamatsu Plant of Catalyst Chemicals Co., Ltd. (72) Inventor Toshiro Komatsu No. 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka 4F100 AA02A AA03 AA17A AA20 AA21A AA28A AA29A AA33A AB22A AT00B BA03 BA07 CC00A DE01A EH462 EJ862 GB41 JA11A JA20A JD08 JG01A JG03 JG04 JM02C JN01C JN18C4G04 A04 0 5G307 AA08 FA01 FA02 FB01 FC08 5G323 BA02 BB01

Claims (7)

[Claims] 1. Crystalline conductive fine particles having a porosity in the range of 0.10 to 0.60 ml / g. 2. The method according to claim 2, wherein the crystalline conductive fine particles are tin oxide, S
2. The crystalline conductive fine particles according to claim 1, wherein the conductive fine particles are tin oxide, indium oxide, Sn or F-doped indium oxide, antimony oxide, low-order titanium oxide, or a mixture thereof. 3. The method for producing crystalline conductive fine particles according to claim 1, comprising the following steps (a) to (e). (a) adding a doping agent, if necessary, to an aqueous solution of a metal salt, adding an alkali thereto and hydrolyzing the same to prepare hydrated oxide particles or doped hydrated oxide particles of the metal (b) ) A step of filtering and washing the hydrated oxide particles or the doped hydrated oxide particles; (c) dispersing the washed hydrated oxide particles or the doped hydrated oxide particles in water; (D) filtering out the hydrated oxide particles or the doped hydrated oxide particles from the aged dispersion, and drying (e) the dried hydrated oxide particles or the doped hydrated oxide Firing the particles at 200-800 ° C. 4. The method according to claim 1, wherein the metal salt is a metal salt of one metal selected from Sn, In, Sb and Ti, and the doping agent is S
4. The method for producing crystalline conductive fine particles according to claim 3, wherein the compound is a compound containing one element selected from b, F, and P. 5. A coating solution for forming a transparent conductive film, comprising the crystalline conductive fine particles according to claim 1 and a polar solvent. 6. A substrate, a transparent conductive fine particle layer containing the crystalline conductive fine particles according to claim 1 on the substrate, and a transparent conductive fine particle layer provided on the transparent conductive fine particle layer. A substrate with a transparent conductive coating comprising a transparent coating having a lower refractive index than the conductive fine particle layer. 7. A display device comprising a front plate made of the substrate with a transparent conductive film according to claim 6, wherein a transparent conductive film is formed on an outer surface of the front plate. .